Thianaphthylthiazolyl disulfides and process for preparing same



Patented Sept. 30, 1952 THIANAPHTHYLTHIAZOLYL DISULFIDES AND PROCESS FOR PREPARING SAME William S. Emerson and Tracy M. Patrick, J12,

'assignors to Monsanto Chemical St Louis, Mo., a corporation of Dela- 'j (1..

lilo glipp lication November 21, 1950,

This invention relates to organic sulfur com pounds and providessnew derivatives of thiazolyl disulfide and a methodof producing the same.

According to the invention there are produced valuable thianaphthylthiazolyl disulfide' compounds by contacting certain 3-haloacetylthianaphthene oompidfliids' withamm foniuxnidithio oarbamatefsubstantially according to thescheine:

ln which Rand ia'l a selected: class consisting of hydrogen, chlorine, :broi'nine and alkylradicals of from Ito-'4 carbon atoms and X is selected from the class consisting of chlorine andbromine; .As' illustrative of 3-halo'acetylthi'anaphthenes whichmay be reacted with'amrn'dnium dithiocarbamatemay be mentioned 3- chloroacetylthianaphthene or'3-bromoacetylthianaphthene" to yield 4 (3-thian'aphthyll 2. thia-'- zolyl' disulfidey 5=-' methyl-3-'chloroaoetylthimnaphthene to yield 4+(fi methyl ii thianaphth'yl) -2-thiazoly1' "disulfide, 6-butyl 3-brb'fnoacetylthianaphthene to yield 4- (6"-butyl--3'-th ianaphthyl) -2-thiazolyl 'disulfide, '2 -chloro-'-3-chlo'- roacetylthianaphtheneto yield 4-(2-chloro-3' -thianaphthyl) 2-thiazolyl :clisulfide; 5-chloro'-2- 'methyl-3 chloroacetylthianaphthene to yield 4- (5'- chloro-2-- methyl-3 thian'aphthyl) 2 thia- The 3-haloacetylthianaphthenes are readily obtainable by chlorinatingor brominating 3-acetylthianaphthene with the appropriate halogen, at'lowtemper'atures and in the presence of 'a solvent such as chloroform, carbon tetrachloride, etc.

' Reaction or the haloacet lthianaphtheneswith ammonium'dithioca'rbamate to yield the present thi'anaphthylthiazolyl disulfides is effected .substantially as follows: The react ts are gradually added to an inert 1iduid 'dihie p H temperature or with cooling. Since the reaction, liberates some heat and generally rai t t m; perature, ordinarily no extraneous-heat needtbe applied.- Themixt'ure is then allowed to stand at roomtemperature for a time of say, several ither at room' mat ;-Se 1ialNo. 196,951

4 irearm. (011260- 309 :hoursto a week or longer depending upon" the reactivity of the halide. The slurry of disulflde which is formed in the reaction mixture'niaybe recovered by treating the mixture withice, dilutingwi'th water and filtering. The precipitated di fide may t e eiur he purif ed .by W5 ing, drying, and if desired, by recrystallizing from a solvent such as benzene.

Good yields of the thianaphthylthiazolyl disulfides are generally obtained irrespective of thereactant proportions employed. In order to assure complete reaction of.the lessreadilyavailab le haloacetylthianaphthene, however, it is advan: tageous to employ; an excess of the dithio'ca'rbaQ- The quantity of solvent-or suspending agent employed is likewise immateriaL-though care should be employed to use suiilcientdiluent topermit thoroughsolution or adequate suspen sion of the reactants;

Any polar solventor suspending medium which is inert with respect to the reacting constituents or product may be ,employed;-- Suitable solvents may-be, e; g-., ethanol, methanol, isopropanol,

water, dioxane, ethylene glycolypropylene glycol, the monoalkyl ethers of the glycol such asethylene glycol monomethyl ether, etc

The present thianaphthylthiazolyl'. dlsulfides are stable, rather high-melting crystalline to waxymaterials. which may be advantageously employed for a variety of industrial uses. 3 .lfhey may be advantageously employed as petroleum lubricant additives, as modifiers in the preparation of synthetic rubbers and as medicinals; and they are particularly valuable as intermediates for the preparation of rubber vulcanizationaccelerators, Thus as disclosed'in' our 'copending application, Serial No. 196,953, filedNovembei-Zl, 1950, upon treatment of the present disulfijjdes with a reducing agent they are easily converted to give essentially quantitive yieldsjof-thiana'ph- 'thylmercaptothiazoles, which compounds 3 are very valuable rubber vulcanization acee1era tors'.

The invention is further illustrated, butinot limited,vby the followin -example, Q

Example lization from a mixture of benzene and ethanol" raised the melting point to 2221-1223 .C.- Dilution of the original filtrate with hexane precipitated 4.5 g. of crude 4-(3-thianapl ithyl) .2-..t hi& Q. y1

' ..in. WhiqhR and R are selected from the class consisting of hydrogen, chlorine, bromine and disulfide, M. P. 109-117 c. .izr e solid whlchhad been filtered from the original hot benzene .8115}- pension was crystallized from a mixture of ethanol and dioxane. Two crops were collected: I, 10.5 g., M. P. 126l27 C. and'II; 2,0 gi; ""M'..-P; 1l6-120 C. The total yield of crude 4-(3-th-ia-'- naphthyl)-2-thiazolyl disulfide was 17- g. 169%). When a sample of fraction I was crystallized successively from benzene, ethanol and dioxanaand .benzene and'ethanol, the, melting pointrem'ained thesame.,-

Calcd.for r m Qu hNzSa F maul-c 53:2 '53. Percent H. "2. 42 2:24

H Operating-as in the'above example other haloacetylthianaphthenes, e. g. 3-bromoacetylthianaphthene, 2 methyl 3' -'-chloroacetylthianaphthene -or F5-chloro-3-chloroacetylthianaphtheirs-may be similarly reacted with ammonium 'ditliiocarbamate to yield {the :correspondingly substitutedfthianaphthylthiazolyl disulfides; Also, instead "of ethanol other non-reactive polar 'liquids may be employed as suspending media for thereactants. When the thianaphth'ylthiazolyl disulfides are to be 'employedfor the preparation of "thianaphthylmercaptothiazoles, careful purificatio'n of the disulfides asshownin the example, need not'be employed, since the major impurity in the crud'e'disulfide is generally the thianaphthylmercaptothiazole. I 1

What we claim is: l 1-. Disulfi'des havingthe-ge'neral formula in-which Rand R are selected from .the class consisting of, hydrogen, chlorine, bromine and alkyl radicals of from 1 to 4 carbon atoms.

.2. :4.-(3-thianaphthyl) -2-thiazoly1 disulfide.

3. 4 .(6' -chloro-3'-thianaphthyl) 2 thiazolyl disulfide.

.4. 4;-- (6'-.methyl-3-thianaphthyl) 2 thiazolyl .disulfide.

5. .4, 5'-me.thy1-3'-thianaphthyl) 2 .thiazolyl disulfide.

6. 4 (4'-chloro-3'-thianaphthyl) 2 thiazolyl disulfide. 7. The method which comprises contacting ammonium dithiocarbamate with a haloacetylthianaphthenehaving the general formula GO CH'zX a elected from the ,class w. ill} OOGHiX" n..which..R and R are sele d :fr m the .class consisting .ofhydrogen, chlorine, bromine and alkyl radicals of from 1 to 4 carbpn atoms and X is selected from the class consisting of chlorine and -bromine, allowing theresulting mixtureto stand until formationof -adi'sulfide having the general formula v in which R and R are selected from the class consistingof hydrogen, chlorine, bromine :and alkyl radicals ,of from 1 to 4 carbon atoms, and recovering said disulfide from the resulting, r eaction'product. 9. .The method which comprises contacting 3-chloroacetylthianaphthene with ammonium dithiocarbamate inthe presenceofan inert liquid diluent, allowing thelresulting 'mixture' to stand until, formation of 4'- (3.-thianaphthyl). .-:2- thiazolyl disulfide and recovering said disulfide from the reaction product. 0'

10-. --The method which comprises contacting 3-bromoacetylthianaphthene with ammonium dithiocarbamate in the presence of an inert'liquid diluent, allowing the resulting mixture to stand until formation of 4-(3-thianaphthyl).-'2- thiazolyl disulfide and recovering saiddisulfide from the reaction product; 11. The method which comprises contacting 3- chloroacetyl-6-chlorothianaphthene with ammonium dithiocarbamate. in the presence-of an in-- ert liquid diluent, allowing the resultingmixture to stand until formationof 4-(6'.-.chloro,e;3'-.-thianaphthyl) -2-thiazolyl disulfide' and recoverin said disulfide from the reaction product.

12. The method which comprises contacting 3-chloroacetyl G-methylthianaphthene with ammonium dithiocarbamate inqthe presence of an inert liquid diluent, allowing the resulting-1mmture to stand-until tormation of 4 -(6- methylj-.8'... thianaphthyl) 2-thiazolyl disulilde andrecovering said disulfide from thereactiqn product. I If." 13. The method which comprises contactingiiichloroacetyl-5 methylthianaphthene witl am moniuzn .dithiocarbamate in the presence. of; an

inert liquid diluent, allowing the resulting mix- REFERENCES CITED ture to stand until formation of 4-(5'-methy The following references are of record in the 3-th1anaphthyl)-2-th1a.zolyl disulfide and refile of this patent: covering said disulfide from the reaction product.

14. The method which comprises contacting 3- 5 UNITED STATES PATENTS chloroacetyl-4-chlorothianaphthene with ammo- Number Name Date nium dithiocarbamate in the presence of an in 2,196,607 Mathes Apr. 9, 1940 ert liquid diluent, allowing the resulting mixture to stand until formation of 4-(4'-chloro-3'-thianaphthyl) 2-thiazolyl disulfide and recovering 10 said disulflde from the reaction product.

WILLIAM S. EMERSON. TRACY M. PATRICK, JR. 

1. DISULFIDES HAVING THE GENERAL FORMULA 